EP0961798A1 - Process for the polymerization of lactide - Google Patents

Process for the polymerization of lactide

Info

Publication number
EP0961798A1
EP0961798A1 EP98903055A EP98903055A EP0961798A1 EP 0961798 A1 EP0961798 A1 EP 0961798A1 EP 98903055 A EP98903055 A EP 98903055A EP 98903055 A EP98903055 A EP 98903055A EP 0961798 A1 EP0961798 A1 EP 0961798A1
Authority
EP
European Patent Office
Prior art keywords
lactide
polymerization
reactor
polymer
melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98903055A
Other languages
German (de)
French (fr)
Other versions
EP0961798B1 (en
Inventor
Kari Jansson
Jukka Koskinen
Johan-Fredrik Selin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fortum Heat and Gas Oy
Hyflux IP Resources Pte Ltd
Original Assignee
Fortum Oil Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fortum Oil Oy filed Critical Fortum Oil Oy
Publication of EP0961798A1 publication Critical patent/EP0961798A1/en
Application granted granted Critical
Publication of EP0961798B1 publication Critical patent/EP0961798B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

Definitions

  • the invention relates to a two-step polymerization of lactide to polylactide.
  • the inven- tion in particular relates to a process in the second step of which there is carried out polymerization to a high conversion in conditions in which the mixing of the melt and the evaporation of lactide are avoided.
  • biodegradable polymers i.e. biopolymers
  • biopolymers have greatly in- creased, and many companies have made efforts to launch on the market packaging materials, hygiene products, sacks and films for agricultural purposes, and sacks for waste.
  • various films have gained importance.
  • the use of polymers of lactic acid in these applications has so far been limited by the high price of the polymers and their susceptibility to breaking down during technical processing.
  • Polyhydroxy acids can be prepared by polycondensation reactions, which are typical in the preparation of polyesters, or by ring-opening polymerization from cyclic lactones. Polyhydroxy acids are thermoplastic polyesters which resemble many conventional polymers.
  • Polylactides, or condensation polymers based on lactic acid, are for many reasons especially attractive, since their principal degradation product, lactic acid, is a product common in nature, it is not toxic and is used widely in the food and pharmaceutical industries.
  • a high molecular weight polymer can best be produced by ring-opening polymerization from lactide. Lactic acid is optically active, and thus its dimer appears in four different forms: L,L-lactide; D,D-lactide; L,D-lactide (mesolactide); and a racemic mixture of L,L- and D,D-lactides.
  • the ring-opening polymerization of cyclic lactones of hydroxy acids constitutes technology known per se.
  • the polym- erization processes known are various, some examples being patent US 5,378,801 re- lating to extrusion polymerization, patent publication EP 0 664 309- A relating to two- step polymerization, and patent publication EP 0 499 747-A describing polymerization in a mixing reactor.
  • the polymerization velocity of lactide depends on many factors, such as the initiator used, the initiator concentration, the polymerization temperature, and the lactide concentration.
  • the polymerization velocity is significantly dependent on the lactide concentration when the lactide concentration is above 30 % by weight. Within this range also the viscosity of the polymer-lactide blend at the polymerization temperatures commonly used is relatively low, and thus the polymerization can advantageously be carried out in a stirred reactor at the desired polymerization temperature.
  • an advantageous method of polymerizing to a lactide concentration up to approx. 30 % by weight is reactive extrusion polymerization, wherein the monomer and the catalyst are fed continuously into the extruder.
  • the monomer polymerizes rapidly within the lactide concentration and temperature ranges concerned, typically within approx. 2 minutes to a conversion of 30 % by weight.
  • the polymerization apparatus used in the second polymerization step is a heated pipe within which the polymer melt travels.
  • the pipe walls are typically heated to a temperature of 180 - 250 °C, and the retention time is 1 - 10 min.
  • the mixing of the polymer melt in the pipe is very slight.
  • the apparatus according to this embodiment is shown in Figure 1.
  • Preferred embodiments of other types include a heated conveyor in which the polymer melt is conveyed in a pressurized and heated space on a sheet or a metal belt, from which it is scraped for further processing of the polymer.
  • a heated conveyor in which the polymer melt is conveyed in a pressurized and heated space on a sheet or a metal belt, from which it is scraped for further processing of the polymer.
  • Figure 2 One typical apparatus of this embodiment is shown in Figure 2.
  • the second reactor used in the process according to the invention is highly economical.
  • the molar mass of the polymer does not rise during the second polymerization step even though the lactide is capable of reacting with the polymers present and the conversion reaches a high level.
  • the polymer or copolymer according to the present invention can be prepared from L- lactide, D-lactide or D,L-lactide, or blends thereof.
  • Conventional initiators suitable for lactide polymerization such as various tin and iron compounds, can be used in the polymerization.
  • the molar mass (M w ) of the polymer is approximately 20000-500000, preferably 40000-300000.
  • the polymer is prepared from L-lactide.
  • the first step of the polymerization can be carried out advantageously by extrusion polymerization.
  • the polymer is produced by heating the monomer or the monomer blend to produce a homogeneous melt and by adding a catalyst in order to polymerize the lactide, whereupon the ring opens. It is also possible advantageously to mix the catalyst and the lactide together while cold and to feed the blend into the extruder.
  • the pipe walls were heated by means of an oil jacket to a temperature of approx. 220 °C, and the pressure resistance of the pipe was of the order of 1000 bar.
  • the average retention time of the polymerizing lactide melt in the pipe system was approx. 2 min, the concentration of lactide in the polymer being less than 10 % by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Materials For Medical Uses (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

A two-step process is described for the polymerization of lactide to polylactide, in which process in the first step polymerization is carried out to a conversion of at least 50% by weight, and in the latter step the polylactide is polymerized further to a high conversion in conditions in which the mixing of the melt and the evaporation of the lactide are avoided.

Description

Process for the polymerization of lactide
The invention relates to a two-step polymerization of lactide to polylactide. The inven- tion in particular relates to a process in the second step of which there is carried out polymerization to a high conversion in conditions in which the mixing of the melt and the evaporation of lactide are avoided.
In recent years, interest in biodegradable polymers, i.e. biopolymers, has greatly in- creased, and many companies have made efforts to launch on the market packaging materials, hygiene products, sacks and films for agricultural purposes, and sacks for waste. In particular, various films have gained importance. The use of polymers of lactic acid in these applications has so far been limited by the high price of the polymers and their susceptibility to breaking down during technical processing.
Polyhydroxy acids can be prepared by polycondensation reactions, which are typical in the preparation of polyesters, or by ring-opening polymerization from cyclic lactones. Polyhydroxy acids are thermoplastic polyesters which resemble many conventional polymers.
Polylactides, or condensation polymers based on lactic acid, are for many reasons especially attractive, since their principal degradation product, lactic acid, is a product common in nature, it is not toxic and is used widely in the food and pharmaceutical industries. A high molecular weight polymer can best be produced by ring-opening polymerization from lactide. Lactic acid is optically active, and thus its dimer appears in four different forms: L,L-lactide; D,D-lactide; L,D-lactide (mesolactide); and a racemic mixture of L,L- and D,D-lactides. By polymerizing these either as pure compounds or at different blend proportions, polymers are obtained which have different stereochemical structures affecting their resilience and crystallinity and, consequently, also their me- chanical and thermal properties. The obtained polymers are usually hard and optically bright.
The ring-opening polymerization of cyclic lactones of hydroxy acids, such as lactide, glycolide, epsilon caproiactone, etc., constitutes technology known per se. The polym- erization processes known are various, some examples being patent US 5,378,801 re- lating to extrusion polymerization, patent publication EP 0 664 309- A relating to two- step polymerization, and patent publication EP 0 499 747-A describing polymerization in a mixing reactor.
It is typical of the prior known art that the residual lactide concentration is high, which hampers the processing of the polymer and, on the other hand, its removal causes additional costs.
It is an object of the invention to find a method for the polymerization of lactide, pref- erably to a conversion which is close to the theoretical maximum. The polymerization velocity of lactide depends on many factors, such as the initiator used, the initiator concentration, the polymerization temperature, and the lactide concentration.
The polymerization velocity is significantly dependent on the lactide concentration when the lactide concentration is above 30 % by weight. Within this range also the viscosity of the polymer-lactide blend at the polymerization temperatures commonly used is relatively low, and thus the polymerization can advantageously be carried out in a stirred reactor at the desired polymerization temperature.
During the development of the process it was observed that an advantageous method of polymerizing to a lactide concentration up to approx. 30 % by weight is reactive extrusion polymerization, wherein the monomer and the catalyst are fed continuously into the extruder. The monomer polymerizes rapidly within the lactide concentration and temperature ranges concerned, typically within approx. 2 minutes to a conversion of 30 % by weight.
It has now been observed, surprisingly, that, in order to polymerize of lactide to a high conversion and to a low lactide concentration, it is preferable to carry out further polymerization in an apparatus in which the polymer melt is polymerized to as high a degree as possible in conditions in which there occurs no transfer of material. Efforts are made to prevent the evaporation of lactide and the mixing of the lactide melt in the apparatus. The polymerization velocity is sufficiently high and the reaction heat of the polymerization is low, so that the lactide will polymerize to a high conversion in a controlled manner within a short period. According to a preferred embodiment of the invention, the polymerization apparatus used in the second polymerization step is a heated pipe within which the polymer melt travels. The pipe walls are typically heated to a temperature of 180 - 250 °C, and the retention time is 1 - 10 min. The mixing of the polymer melt in the pipe is very slight. The apparatus according to this embodiment is shown in Figure 1.
It is also possible to apply in the polymerization other systems with the polymerization conditions of the type described above. Preferred embodiments of other types include a heated conveyor in which the polymer melt is conveyed in a pressurized and heated space on a sheet or a metal belt, from which it is scraped for further processing of the polymer. One typical apparatus of this embodiment is shown in Figure 2.
The second reactor used in the process according to the invention is highly economical.
Typically the molar mass of the polymer does not rise during the second polymerization step even though the lactide is capable of reacting with the polymers present and the conversion reaches a high level.
The polymer or copolymer according to the present invention can be prepared from L- lactide, D-lactide or D,L-lactide, or blends thereof. Conventional initiators suitable for lactide polymerization, such as various tin and iron compounds, can be used in the polymerization. The molar mass (Mw) of the polymer is approximately 20000-500000, preferably 40000-300000. Preferably the polymer is prepared from L-lactide.
The first step of the polymerization can be carried out advantageously by extrusion polymerization. The polymer is produced by heating the monomer or the monomer blend to produce a homogeneous melt and by adding a catalyst in order to polymerize the lactide, whereupon the ring opens. It is also possible advantageously to mix the catalyst and the lactide together while cold and to feed the blend into the extruder.
The invention is described further in greater detail with the help of the following examples. Example 1
A polymer melt polymerized in an extruder to a conversion of approx. 70 % by weight, still containing initiator, was fed at a temperature of approx. 200 °C by means of a melt pump into a pipe equipped with a heating jacket and having a length of 2-3 m. The pipe walls were heated by means of an oil jacket to a temperature of approx. 220 °C, and the pressure resistance of the pipe was of the order of 1000 bar.
The polymer melt polymerized in the pipe system at a high pressure without the evapo- ration of the lactide, the melt traveling in the pipe system in laminar flow conditions. The average retention time of the polymerizing lactide melt in the pipe system was approx. 2 min, the concentration of lactide in the polymer being less than 10 % by weight.
Prepolymerization was carried out by extrusion polymerization to various lactide con- centrations. The results of the second polymerization are compiled in Table 1.
Table 1.

Claims

Claims:
1. A two-step process for the polymerization of lactide to polylactide, in which process in the first step the polymerization is carried out to a conversion of at least 50 % by weight, characterized in that in the latter step the polylactide is polymerized further to a high conversion in conditions in which the mixing of the melt and the evaporation of the lactide are avoided.
2. A process according to claim 1, characterized in that the temperature in the latter reactor is 180-250 ┬░C.
3. A process according to claim 1 or 2, characterized in that the retention time in the reactor is 1-10 min.
4. A process according to claims 1-3, characterized in that the reactor is a pipe equipped with heating, withstanding high pressure.
5. A process according to any of the above claims, characterized in that the reactor is a pressurized and heated polymerization apparatus equipped with a belt conveyor.
EP98903055A 1997-02-14 1998-02-13 Process for the polymerization of lactide Expired - Lifetime EP0961798B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI970651 1997-02-14
FI970651A FI107337B (en) 1997-02-14 1997-02-14 A method for polymerizing lactide
PCT/FI1998/000135 WO1998036008A1 (en) 1997-02-14 1998-02-13 Process for the polymerization of lactide

Publications (2)

Publication Number Publication Date
EP0961798A1 true EP0961798A1 (en) 1999-12-08
EP0961798B1 EP0961798B1 (en) 2004-08-18

Family

ID=8548218

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98903055A Expired - Lifetime EP0961798B1 (en) 1997-02-14 1998-02-13 Process for the polymerization of lactide

Country Status (9)

Country Link
US (1) US6214967B1 (en)
EP (1) EP0961798B1 (en)
JP (1) JP2001513121A (en)
KR (1) KR20000071024A (en)
AT (1) ATE274013T1 (en)
AU (1) AU5991498A (en)
DE (1) DE69825728T2 (en)
FI (1) FI107337B (en)
WO (1) WO1998036008A1 (en)

Families Citing this family (17)

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Publication number Priority date Publication date Assignee Title
FI122108B (en) 2004-11-17 2011-08-31 Jvs Polymers Oy Crosslinking biopolymer
MX2009000527A (en) 2006-07-14 2009-01-27 Kimberly Clark Co Biodegradable polyactic acid for use in nonwoven webs.
US8710172B2 (en) 2006-07-14 2014-04-29 Kimberly-Clark Worldwide, Inc. Biodegradable aliphatic-aromatic copolyester for use in nonwoven webs
EP2044251B1 (en) 2006-07-14 2019-10-02 NatureWorks LLC Biodegradable aliphatic polyester for use in nonwoven webs
KR100793903B1 (en) * 2006-12-21 2008-01-15 호남석유화학 주식회사 Process for preparing lactones biodegradable solid polymer and apparatus for preparing the same
US8518311B2 (en) 2007-08-22 2013-08-27 Kimberly-Clark Worldwide, Inc. Multicomponent biodegradable filaments and nonwoven webs formed therefrom
EP2031009A1 (en) * 2007-09-03 2009-03-04 Uhde Inventa-Fischer GmbH Cleaning device for separating dilactide from a materials mixture, polymerisation device, method for separating dilactide from materials mixtures and application
AT506038B1 (en) 2007-11-14 2015-02-15 Jungbunzlauer Austria Ag METHOD FOR THE PRODUCTION OF CYCLIC DIESTERS OF L, D AND D, L-MILKYLIC ACID
AT506768B1 (en) 2008-04-16 2013-10-15 Jungbunzlauer Austria Ag METHOD FOR CLEANING CYCLIC DIESTERS OF L- BZW. D-LACTIC
CN102046861B (en) 2008-05-30 2012-12-12 金伯利-克拉克环球有限公司 Polylactic acid fibers
PL2310437T3 (en) * 2008-07-31 2016-03-31 Purac Biochem Bv Process for the continuous production of polyesters
CN101665566B (en) * 2008-09-01 2012-01-04 南京工业大学 Method for preparing polylactic acid and products thereof by utilizing double-screw extruder
US8461262B2 (en) 2010-12-07 2013-06-11 Kimberly-Clark Worldwide, Inc. Polylactic acid fibers
US20120214944A1 (en) * 2011-02-18 2012-08-23 Fina Technology, Inc. Polyolefin polylactic acid in-situ blends
JP5806890B2 (en) * 2011-09-12 2015-11-10 日立造船株式会社 Process for producing semicrystalline polylactide
CN103772667B (en) * 2012-10-23 2016-01-13 中国石油化工股份有限公司 A kind of production method of polylactic acid material
KR101692988B1 (en) 2014-11-27 2017-01-04 롯데케미칼 주식회사 Polylactide resin having improved thermal stability

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US5378801A (en) 1988-11-01 1995-01-03 Reichert; Dieter Continuous process for the preparation of resorable polyesters and the use thereof
US5136017A (en) 1991-02-22 1992-08-04 Polysar Financial Services S.A. Continuous lactide polymerization
DE69509927T2 (en) 1994-01-21 2000-01-27 Shimadzu Corp Method of producing polylactic acid

Non-Patent Citations (1)

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Title
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Also Published As

Publication number Publication date
EP0961798B1 (en) 2004-08-18
US6214967B1 (en) 2001-04-10
DE69825728T2 (en) 2005-08-25
FI107337B (en) 2001-07-13
JP2001513121A (en) 2001-08-28
DE69825728D1 (en) 2004-09-23
KR20000071024A (en) 2000-11-25
ATE274013T1 (en) 2004-09-15
AU5991498A (en) 1998-09-08
FI970651A (en) 1998-08-15
FI970651A0 (en) 1997-02-14
WO1998036008A1 (en) 1998-08-20

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